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The Open Process Chemistry Journal, 2008, 1, 8-11

Open Access

Effect of Irgacure 651 Initiator on Poly(Methyl Methacrylate)


Photostability Studied by UV-Vis Spectroscopy#
Halina Kaczmarek* and Piotr Gaka
Faculty of Chemistry, Nicolaus Copernicus University, 7, Gagarin Str., 87-100 Toru, Poland
Abstract: Commercial initiator 2,2-dimethoxy-2-phenyl acetophenone (Irgacure 651, Ciba, Switzerland) was introduced to poly(methyl methacrylate) (PMMA) matrix to enhance the polymer degradation. Two types of thin polymeric
films (PMMA and PMMA+5% Irgacure) were UV-irradiated in laboratory conditions (Xenon lamp, air atmosphere, room
temperature). The photochemical changes in pure PMMA and PMMA doped with the initiator were studied by absorption
spectroscopy in the UV-Vis range. Separately, the behaviour of the initiator in the acetonitrile (ACN) solution upon UVradiation was investigated at the same conditions. It was found that the addition of the Irgacure 651 to PMMA accelerated
the photooxidative degradation, particularly at the early stages of exposure. The efficiency of formation of chromophoric
groups in PMMA in the presence of the Irgacure initiator was significantly greater than in pure polymer. This suggests
that the free-radical products of the initiator photolysis (mainly benzoyl radicals) are able to abstract hydrogen atoms from
PMMA molecules.

INTRODUCTION
Irgacure photoinitiators constitute a family of commercial compounds, produced by Ciba Specialty Chemicals,
Switzerland. They are well known as efficient intiators of
polymerization of various kinds of monomers [1-7]. Such
initiators as benzyl ketals, ,-dialkoxyacetophenones and
-hydroxyalkylphenones contain chromophoric groups that
absorb radiation in ultraviolet or visible range and undergo
photolysis with formation of free radicals. The photochemical properties and photoinitiation activity of these organic
compounds in polymerization and crosslinking of acrylated
monomers were studied by various experimental methods.
One of the most efficient photoinitiators in this group is Irgacure 651 (DMPA), C6H5-CO-C(OCH3)2-C6H5 [1, 2]. The
compound is characterized by high phosphorescence quatum
yield (=0.62) and relatively long triplet lifetime (1/2=
2.59ms). High polymerization rate and large conversion degree in the presence of DMPA is explained by the significant
benzoyl radical concentration, which was confirmed by flash
photolysis. The initial concentration of the initiator in photopolymerised formulation has a great influence on the molecular weight and polydispersity of the obtained polymer
[8].
Although the photoinitiating action of Irgacure compounds is well documented, the idea of using of these photoinitiators as degrading agents for the purpose of obtaining
of the degradable materials is rather new. Our preliminary
work, considering this topic, gives the promising information
useful for designing the polymeric materials with controlled
life-time.
*Address correspondence to this author at the Faculty of Chemistry, Nicolaus Copernicus University, 7, Gagarin Str., 87-100 Toru, Poland;
E-mail: halina@chem.uni.torun.pl
#

Presented on the 42nd IUPAC World Polymer Congress, Polymers at Frontiers of


Science and Technology, Taiwan, Taipei, 2008.

1875-1806/08

The aim of this presentation is to study the photostability


of poly(methyl methacrylate) (PMMA) doped with 2,2dimethoxy-2-phenyl acetophenone initiator (abbreviation DMPA, trade name - IRGACURE 651) and to compare the
course of photochemical reaction in doped and undoped
polymers using UV-Vis spectroscopy.
MATERIALS AND METHODOLOGY
The poly(methyl methacrylate) (Mw =120000, SigmaAldrich) was used without purification. The photointiator

Irgacure 651 was supplied by Ciba, Basel, Switzerland. The
polymer and the initiator were dissolved in tetrahydrofurane.
Thin polymeric films were obtained by casting the solution
directly onto spectroscopic windows. The modified PMMA
contained 5%(wt) of Irgacure 651.
The polymeric samples were UV-irradiated at room temperature and in air for 1-24h using high pressure xenon lamp
XBO R 180 W/45 OFR with ZXE 180 power supply adaptor
(provided by Optel, Opole, Poland). The intensity of incident
light, monitored by the HD 9021 radiometer (Delta, Italy),
was equal to 35.2 W/cm2 (for UV-A), 9.70 W/cm2 (UV-B)
and 2.30 W/cm2 (UV-C).
The UV-Vis spectra of the pure PMMA and the polymer
doped with DMPA were recorded by UV-1601PC spectrometer (Shimadzu, Japan).
DMPA initiator was exposed to the radiation emitted
from Xenon lamp in acetonitrile (ACN) solutions at different
concentrations. The irradiation and spectroscopic studies
were performed using a quartz cell with a path length of 1
cm.
RESULTS AND DISCUSSIONS
The changes of electronic spectra of Irgacure 651 in
ACN solutions caused by the UV-irradiation are shown in
2008 Bentham Open

Photostability of Modified Poly(Methyl Methacrylate)

The Open Process Chemistry Journal, 2008, Volume 1

Fig. (1). The main bands with the maxima at 205, 251 and
341 nm are present, which is in a good agreement with the
literature data [2]. These bands are attributed to * and
n* transitions.
The Fig. (1A) shows the decrease of the band intensity at
205 and 251 nm with the simultaneous formation of a new
absorption peak at 223 nm during the 20 minutes of exposure. The low-intensity band at higher wavelenght (341 nm)
also disapears rapidly, which is clearly observed in spectrum
recorded for more concentrated solution (Fig. 1B). It indicates that Irgacure 651 undergoes the efficient photolysis in
applied conditions.

the formation of small methyl radical (3) and methyl benzoate (4). Both (1) and (3) radicals participate in photoinitiated
polymerization but the action of CH3 is much less effective
than this of (1). Moreover, other major products of DMPA
photolysis are benzaldehyde, benzil and acetophenone [14].
Benzil, which is diketone (C6H5C=O)2 is also used as a photoinitiator in the polymer curing.
O
C

OCH3
C

C
OCH3

OCH3
DMPA

OCH3

h

(1)

(2)

A
3,0

max. 205nm

unirradiated
30 sec
2 mins
5 mins
10 mins
20 mins

max. 223nm

2,5

Absorbance

2,0

1,0

0,5

0,0
200

250

300

Wavelength [nm]

Absorbance

1,5

unirradiated
30 sec
2 mins
5 mins
10 mins
20 mins

max. 341nm

1,0

0,5

0,0
250

300

350

400

C
(4)

OCH3 +

CH3
(3)

Scheme 1. Photolysis of Irgacure 651 initiator.

The photostability of PMMA and PMMA + Irgacure 651


films of the same thickness were investigated using UV-Vis
spectroscopy. The examples of changes in UV-Vis spectra of
these samples are presented in Fig. (2). As can be noticed,
the band at 251 nm, atributed to the photoinitiator, is present
in the spectrum of the modified PMMA. However, it disapears already in the first hour of UV-irradiation.

max. 251nm

1,5

450

Wavelength [nm]

Fig. (1). The changes in UV-Vis absorption spectra of Irgacure 651


in ACN solutions during UV-irradiation: (A) Cm= 8.8x10-5mol/dm3;
(B) C m= 4.4x10-3mol/dm3.

The carbonyl organic compounds of benzoin type, after


the photon absorption and excitation undergo the dissociation (Norrish type I cleavage) according to Scheme
1. This reaction is very fast and formed benzoyl (1) and ,dimethoxybenzyl radicals (2) differ significantly in their
reactivity [9-13]. The fragmentation of the latter one leads to

The other signals due to initiator are difficult to detect in


PMMA spectrum. The maximum at 205 nm overlaps the
carbonyl band from PMMA; the band at 341 nm, owing to
its low absorption coefficient [8] and because of low DMPA
concentration in polymeric sample is hardly seen.
The prolongation of exposure time causes an increase of
the absorbance in the 200-400nm range. The observed
changes in UV-Vis spectra of both polymeric samples are
irregular - particularly fast increase of the absorbance was
observed at the beginning of the irradiation. The broad absorption band formed during the sample exposure indicates
that the complex mixture of photoproducts arises. The increase of the absorbance in both UV-irradiated samples can
be explained by the formation of the new functional groups
such as carbonyls in main chain and separated or conjugated
double bonds. It is known that PMMA undergoes mainly
depolymerisation but furthermore a random chain scission
takes place [15]. The created monomer and oligomers containing unsaturated bonds accumulated in the matrix additionally increase the absorption of the degraded polymer.
The solvent impurities which are present in both unexposed samples have no significant effect on the photodegradation rate, what was proved in the previous experiment.
However, to investigate the kinetics of chromphore formation more thoroughly and to avoid the possible errors, the
absorbance at 300 nm (which is outside of initiator absorption) was chosen for comparison the behavior of the PMMA
and PMMA + DMPA samples.
Fig. (3) shows the differences in the kinetics of the photochemical reaction leading to the generation of the products
absorbing at 300 nm. The rapid absorbance increase after 1h
irradiation is an evidence of the fast reaction in the first pe-

10 The Open Process Chemistry Journal, 2008, Volume 1

Kaczmarek and Gaka

The enhancement of the photoreaction in the modified


PMMA can be explained by the reaction of the initiating
species from DMPA with macromolecules. Most probable is
the hydrogen abstraction from PMMA (Scheme 2).
O
C

0,12

PMMA
PMMA + 5% Irg. 651

0,10

Absorbance ( = 300nm)

riod of the experiment. The next stage of photooxidative


degradation is significantly restrained. The yield of the
chromophoric group formation in the modified PMMA is a
few times higher that in pure polymer. It is obviously caused
by high concentration of the free radicals formed as a result
of the DMPA decay.

0,08

0,06

0,04

0,02

O
+ PH

+ P

0,00

Scheme 2. Initiation of PMMA decomposition by benzoyl radical.

The macroradical (P) undergoes the secondary reactions,


for example the addition of the oxygen molecules with the
formation of peroxyradicals (POO), which is a typical process for many polymers [15].

unirradiated
1 hour
2 hours
4 hours
8 hours
24 hours

Absorbance

0,75

0,25

300

400

Wavelength [nm]

Fig. (3). The kinetics of chromophore formation in the pure PMMA


and the PMMA containing 5% Irgacure 65 during the exposure to
Xenon lamp.

CONCLUSIONS

ACKNOWLEDGEMENTS

REFERENCES

unirradiated
1 hour
2 hours
4 hours
8 hours
24 hours

1,0

251nm

Absorbance

25

The financial support from a Rector grant (Nicolaus Copernicus University, Toru, Poland, grant number: 561-Ch)
is gratefully acknowledged.

[1]

[2]

0,5

[3]

[4]
0,0
200

20

Photolysis of DMPA in PMMA matrix is slower than in


acetonitrile solution. This is caused by trapping of the initiator in the stiff polymer matrix where the mobility of the
molecules is restricted, contrary to the solution. However,
the concentration of the free radicals formed during the
DMPA photodecomposition is high enough for the initiation
of the macromolecules scission. The photooxidative degradation, leading to the chromophore formation, occurs in the
doped PMMA with the higher rate and efficiency comparing
to the virgin PMMA.

0,50

0,00
200

15

It was found that the presence of smal amount of 2,2dimethoxy-2-phenyl acetophenone in PMMA film accelerates its photodegradation.

A
1,00

10

Time [h]

300

400

Wavelength [nm]

Fig. (2). Changes of UV-Vis spectra of the pure PMMA (A) and
PMMA doped with Irgacure 651 (B) during the exposure to Xenon
lamp.

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Received: July 30, 2008

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Revised: September 30, 2008

Accepted: October 7, 2008

Kaczmarek and Gaka; Licensee Bentham Open.


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